Process of separating vanadium from titanium



Patented Feb. 4,' 1941 l a v I UNITED STATES PATENT OFFICE PROCESS OF 4 Leslie G. Jenness, Englewood, and Roger L.

Annis, Newark, N. J., assignors, by mesne assignments, to Vanadium Corporation of America, New York, N. Y., a corporation of Delaware No Drag. Application March-20, 1940, Serial No. 325.068

9 Claims. (Cl. 23-87) This invention relates to the separation of has, heretofore, been commercially impracticable vanadium from titanium, and more particularly to produce such white titanium oxide from. vanato a process in which compounds of vanadium dim-contaminated titanium ores or compounds, are formed which are readily separable from since the vanadium content rendered thetita titanium tetrachloride. niurn oxide brown in color. 5

Commercially available titanium compounds In accordance with the present invention, it almost invariably contain small quantities of has been found that the organic compounds revanadium compounds. Titanium ores, in genferred to polymerize when added to a mixture of eral, contain vanadium. No commercially practitanium tetrachloride containing vanadium, and 10 ticable method for separating vanadium comreact with the vanadium during polymerization 10 pounds from titanium compounds has heretofore to form compounds which are easily separable been known. Vanadium-free titanium comfrom the titanium tetrachloride, leaving vanapounds have many useful applications in the arts, dium-free titanium tetrachloride. Other organic but the commercial titanium compounds, as well compounds either vdo not react in the titanium as the titanium ores referred to, could not be emtetrachloride-vanadium solution or react with the 15 ployed for the commercial preparation of vanatitanium tetrachloride without reacting with the dium-free titanium compounds. vanadium. The present invention is concerned The present invention, however, provides a' with organic materials which polymerize in the simple economical method of making this separapresence of titanium tetrachloride containing tion. 1 vanadium while reacting with the vanadium to 20 Titanium compounds or the titanium/content form compounds readily separable from the titaof ores can, in general, be easily converted into niurn tetrachloride. titanium tetrachloride, which is a volatile liquid It s. thereforean Object of the Present at ordinary temperatures and pressures, by treatvention to i provide a simple and economical ing the titanium compounds with chlorine or process of removingvanadium from titanium 25 chlorine in the presence of sulfur higher chlocomp r rides, the sulfur chlorides functioning as reduc- 'Another object of the present invention is to ing agents. Vanadium contalned in titanium provide a process of removing vanadium from compounds or ores appears in solution in the titanium compounds in which a material is resulting titanium tetrachloride even though the added to titanium tetrachloride containing vana- 30 titanium tetrachloride be distilled from the reacdium 110 f rm a mp with the Vanadium tion zone in which it is formed. The vanadium which can be easily sep from the titanium is believed to be present in the form of vanadium tetrachlori oxychloride or vanadium tetrachloride, both of A further object of t e invention s to P v which are volatile liquids at ordinary temperaa process of removing vanadium from titanium 35 tures and pressures. However, the exact form of tetrachloride containing vanadium in which an the vanadium insolution in the titanium tetraorganic material is added to the mixture to form chloride is not material to the present invention. a non-volatile comp with the Vanadium Repeated fractional distillation or other known from which the titanium tetrachloride can be diso methods of separation are ineffective to remove tilled. 0 the vanadium from the titanium tetrachloride. Ordinary rubber is an example of an organic It has been discovered that the addition of material which, when added to titanium tetrasmall amounts of certain organic materials causes chlori containing V n W react with the the formation of vanadium compounds which are vanadium to form a solid comp which is 5 solid, insoluble in the titanium tetrachloride, and non-vo atile a e b i P t Of the titanium non-volatile at or considerably above the boiling tetrachloride. R ubber is already partly polymerpoint of titanium tetrachloride. These comized. but further polymerization takes place propounds can therefore, be separated from the ducing a black, brittle solid,usaully granular or titanium tetrachloride by distilling the titanium in the form of a powder. The resultant rubbertetrachloride from the compounds, or by such vanadium compound may be separated from the 50 mechanical methods as filtering orcentrlfu'ging. titanium tetrachloride either by distilling the Thus, vanadium-free titanium tetrachloride is titanium tetrachloride from the resultant mixproduced which may be easily converted into ture or filtering or centrifuging the rubber-vanaother titanium compounds, for example, a pure dium compound from the titanium tetrachloride. white titanium oxide suitable for pigments. It For example, vanadium-free titanium tetrachlo- 55' the effectiveness of the rubber. also indicate that the rubber is the active invanadium have been'found eilective to provide for the removal of vanadium from titanium tetrachloride. The following table lists a series of materials which are effective.

Table I Percent V' Percent V Substance zfiggg originally in distilled present titanium Rubber (pure smoke sheet) 25 070 000 Rubber (acid cured)... 25 070 000 Rubber vulcanized). 50 070 .004 Balata (resin free) 25 070 000 Art gum 25 070 000 Polymerized sulionated oil 50 070 000 Soy bean oil 50 070 000 Cottonseed etearine (IV3.67) 50 070 000 Russianmineral oil (trade name "Volga il) 2.0 .070 .000 Russian mineral oil (trade name "Volga Oil) 0 070 009 acid cured rubber, and resin-free balata, in

amounts equal to 0.25% of the vanadium-titanium tetrachloride mixture was eiiective to completely prevent the vaporization of vanadium compounds. However, 0.50%- vulcanized rubber did not completely prevent the vaporization of vanadium compounds, as shown by the fact that 0.004% vanadium was found in the distillate. This indicates that there is an actual compound formed between the vanadium and the rubber, since the presence of sulfur in combination with the rubber due to vulcanization evidently reduced These results gredient, since resin-free balata also was effective to produce vanadium-free titanium tetrachloride.

It was also found that art gum, which is understood to be primarily polymerized suifonated oil, was eflective to produce vanadium-free titanium tetrachloride when added in an amount equal to 0.25%. To check this result, a quantity of polymerized sulfonated oil was tried, and, as shown by the table, was also efi'ective to produce vanadium-free titanium tetrachloride. These materials also polymerized to a black brittle solid or a black powder during the reaction. Since the polymerized sulfonated oil is derived from glyceride oils, soya bean oil was tried and was also found effective. It was noted, however, that the soya bean oil first formed an orange-colored, rubbery mass, which indicated polymerization, before becoming dispersed in the titanium tetrachloride containing vanadium and then further polymerizing to a solid similar to the materials discussed above. Soya bean oil contains large amounts of unsaturated fatty acid radicals, and

to determine the effect-of unsaturation, a. quantity of cottonseed stearine having an iodine number of only 3.67 was employed, and was found to be effective, indicating that unsaturated glycerides were not essential. This material also formed a rubbery mass prior to dispersion in the solution and further polymerization. It is believed that the titanium tetrachloride first reacts with the unpolymerized organic material whilecausing polymerization and forms compounds in which the vanadium replaces the titanium during further polymerization.

A material containing saturated cyclic compounds was then employed. Such a material was found in Russian mineral oil, sold under the trade name Volga Oil, which is a highly refined petroleum product containing large amounts of naphthenic compounds such as cyclic hexane and its derivatives. As shown by the table, this material was also eflective in amounts equal to 2% of the titanium-vanadium solution and also rendered the majority of the vanadium by the following table, were not eflective.

Table II I Percent V Percent V Substance 3323 originally in distilled present titanium 2.0 .010 .010 a o 070 .011 .00 2.0 .070 .068 Activated carbon 2.0 070 072 common to the various compounds. It is obvious that none of these substances allow the. formation 01' an addition or substitution compound with titanium or vanadium.

Certain other cyclic compounds, and compounds which it was believed might polymerize in the presence of the titanium tetrachloridevanadium solution were then tried. For example, benzaldehyde, which is a cyclic compound having an aldehyde radical attached thereto, reacted with the titanium tetrachloride and was precipitated from the solution. Glycerine and ethyl alcohol, both of which are straight'chain compounds containing alcohol radicals, also reacted with the titanium tetrachloride, and precipitated from the solution. Thus, none of these compounds were eflective to combine with the .solution.

product was observed at approximately C. to C. At 100 C. sublimation ceased and the acetylene was entirely polymerized into a rubberlike product. This product dispersed in the solution and further polymerized during reaction with the vanadium and enabled vanadium-free titanium tetrachloride to be distilled from the The above described experiments indicate that the removal of vanadium is dependent uponthe presence of a material which readily forms ad-- dition or substitution products with vanadium in titanium tetrachloride. All of the compounds eifective for this purpose, thus far found, polymerize in the presence of the titanium tetra.

chloride containing vanadium. It also appears that titanium tetrachloride is a good polymerizing agent. The action during polymerization chloride and the formation of a finally polymerized product.

The above reactions between titanium tetra chloride and vanadium can be separately per-.

formed. Adding any of the materials listed in Tab'1e I as well as acetylene directly to vanadium oxychloride in the absence of titanium produces polymerization but at an extremely low rate. Adding these materials to titanium tetrachloride in the absence of vanadium apparently causes a reaction with titanium tetrachloride to take place. This is clearly apparent with the materials which are originally unpolymerized. For example, soya bean oil rapidly polymerizes in the titanium tetrachloride into an orange-colored rubbery material, containing titanium and resembling art gum. The other unpolymerized substances such as cottonseed stearine-and Russian mineral oil and acetylene also rapidly form such gummy substances. Titanium tetrachloride also appears to react with the materials such as rubber and polymerized sulphonated oil, which are already at least partly polymerized. Upon removal from the titanium tetrachloride they likewise contain titanium. All of the products resulting from treatment with titanium tetra chloride when added to .vanadium oxychloride immediately further polymerize to a black brittle solid, usually in the form of a powder, and combine with vanadium while liberating titanium.

Both reactions rapidly take place in titanium tetrachloride containing vanadium. If sufiicient vanadium is present to complete the reaction, the polymer is inert to further reaction with vanadium. Vanadium can be quantitatively recovered from the resulting polymer.

The polymer also contains chlorine, the atomic ratio of vanadium to chlorine being 1:2. Heating the polymer in an atmosphere of inert gas at a temperature as high as 138 C. does not cause any volatilization of vanadium or separation of chlorine Heating in the presence of air at a temperature of 36 to 40 C. causes volatilizatlon of all or the chlorine and two-thirds of the vanadium as VOCla. If chlorine is added to the atmosphere of air, all of the vanadium is volatilized as VOCla. Removal of the vanadium does not materially change the appearance of the polymer and still leaves it inert to further reaction with vanadium. If insufiicient vanadium-were originally present to complete the reaction, the partly reacted polymer, eitherbefore or after removal of vanadium, can be reused for vanadium removal until its afiinity for vanadium is completely satisfied.

It is apparent that there are a large number of organic compounds capable ofbeing employed as vanadium removing agents. The common property of these compounds appears to be that they polymerize in titanium tetrachloride containing vanadium while combining with vanadium: I p r It has been. found that the extent of removal is dependent upon time, temperature and percent of reagent employed. This is shown by the following table, when balata was used'as the vanadium removal agent.

I Tcmpcra-- Percent V Percent V Pfrcent bahta Time ture, C. original loft 0.10 1 hr 136 .070 .018 0.25 1 hr 136 .070 .000 0.50 15 min 136 070 000 0.50 16 hrs. 20 070 070 When .only 0.10% balata was employed, refluxing for one hour at a temperature of 136 C. followed by distillation of titanium tetrachloride did not entirely eliminate vanadium from the titanium tetrachloride. However, 0.25% balata produced a vanadium-free titanium tetrachloride. Also, 0.50% balata produced vanadiumfree titanium tetrachloride after only fifteen minutes refluxing at a temperature of 136 C., while :the same amount of balata in contact for sixteen er than the temperature for balata, but is merely intended to show that the reaction is more rapid at elevated temperatures and that the tempera ture must be suificiently high and the time of reaction sufiiciently long to cause a relatively stable compound to be formed with the vanadium content.

Thus the present invention provides a simple and economical method of removing vanadium .from titanium compounds. Commercial titanium compounds, as Well as titanium ores containing vanadium, can be converted into titanium tetrachloride containing vanadium by known processes. The resulting mixture may then be treated as above described, to produce vanadium-free titanium tetrachloride and then, if desired, converted into the original or other compounds.

Furthermore, the vanadium can be separately recovered from the material separated from the titanium tetrachloride as substantially pure vanadium oxychloride which can likewise be con- .that the invention is not limited to the details disclosed, but may bevaried within the scope of the following claims.

We claim:

1. The process of removing vanadium from titanium compounds, which comprises, adding to titanium tetrachloride containing vanadium, an

"from said titanium tetrachloride.

2. The process of separating vanadium irom a titanium compound containing vanadium; which comprises, converting said compound into titanium tetrachloride containing vanadium, adding thereto an organic compound which will polymerize in said titanium tetrachloride in the presence of vanadium while reacting with said vanadium to form a polymer which is non-volatile at the boiling point of said titanium tetrachloride, causing said compound to form said polymer containing said vanadium, and distilling said titanium tetrachloride from said polymer.

3. The process of separating vanadium from titanium tetrachloride containing vanadium, which comprises, adding thereto an organic material which will polymerize in said titanium tetrachloride in the presence of vanadium while reacting with said vanadium to form a solid non-volatile polymer containing said vanadium, said organic material being added in sufllcient amount to combine with substantially all ofsaid vanadium, heating the resulting mixture to a temperature sumcient to cause said material to polymerize and react with said vanadium, and separating said polymer containing said vanadium from said titanium tetrachloride.

4. The process of separating vanadium from titanium tetrachloride containing vanadium which comprises adding thereto an organic material which will polymerize in said titanium tetrachloride in the presence of vanadium to form a solid non-volatile polymer containing said vanadium, subjecting the resulting mixture to a temperature suflicient to cause said material to polymerize and combine with vanadium, and separating said polymer containing said vanadium from said titanium tetrachloride.

5. The process of separating vanadium from titanium tetrachloride containing vanadium, which comprises, adding thereto an organic masuiiicient to cause said rubber to polymerize into a polymer containing vanadium, and separating said polymer from said titanium tetrachloride.

7. The process of separating vanadium from titanium tetrachloride containing vanadium,

which oomprises, adding a glyceride oil or fat to said titanium tetrachloride, containing vanadium, reacting said glyceride oil or fatwith said vanadium at a temperature suiiicient to cause said glyceride oil or fat to polymerize into a polymer containing vanadium, and separating said polymer from said titanium tetrachloride.

8. The process of separating vanadium irom titanium tetrachloride containing vanadium; which comprises, adding soya bean oil to said titanium tetrachloride containing vanadium, reacting said soya bean oil with said vanadium at a temperature sufiicient to cause said soya bean oil to polymerize into a polymer containing vanadium, and separating said polymer from said titanium tetrachloride.

9. The process of separating vanadium from titanium tetrachloride containing vanadium, which comprises, adding an organic material containing naphthenic compounds to said titanium tetrachloride containing vanadium, re acting said organic material containing naphthenic compounds with said vanadium at a temperature sufiicient to cause said organic material containing naphthenic compounds to polymerize into a polymer containing vanadium, and separating said polymer from said titanium tetrachloride.

' LESLIE G. JENNESS.

ROGER L. ANNIS. 

